3-(2-Methyl-1,3-benzo­thia­zol-3-ium-3-yl)propane-1-sulfonate monohydrate

Guo-Cui Zhang; Ming Kong; Sheng-Li Li

doi:10.1107/S1600536814011660

. 2014 May 24;70(Pt 6):o714. doi: 10.1107/S1600536814011660

3-(2-Methyl-1,3-benzothiazol-3-ium-3-yl)propane-1-sulfonate monohydrate

Guo-Cui Zhang ^a, Ming Kong ^a, Sheng-Li Li ^a,^*

PMCID: PMC4051035 PMID: 24940284

Abstract

In the title hydrated zwitterion, C₁₁H₁₃NO₃S₂·H₂O, the N—C—C—C and C—C—C—S torsion angles in the side-chain are 171.06 (14) and 173.73 (12)°, respectively. In the crystal, inversion-related molecules are π-stacked with an interplanar separation of 3.3847 (2) Å. O—H⋯O hydrogen bonds link inversion-related molecules with a pair of water molecules to form R ₄ ²(8) rings. The closest S⋯S contact is 3.4051 (15) Å between inversion-related molecules.

Related literature

The crystal structure of a related benzothiazole derivative is described by Lynch (2002 ▶). An analysis of bond angles in the thiazole ring system has been given by Muir et al. (1987 ▶). Applications of benzothiazole derivatives have been described by Vicini et al. (2003 ▶); Bondock et al. (2010 ▶); Paramashivappa et al. (2003 ▶) and Sayama et al. (2002 ▶).

Experimental

Crystal data

C₁₁H₁₃NO₃S₂·H₂O
M _r = 289.36
Monoclinic,
a = 10.936 (5) Å
b = 8.708 (5) Å
c = 13.794 (5) Å
β = 109.529 (5)°
V = 1238.0 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.880, T _max = 0.919
8500 measured reflections
2182 independent reflections
2105 reflections with I > 2sσ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.030
wR(F ²) = 0.080
S = 1.01
2182 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, Global. DOI: 10.1107/S1600536814011660/pk2524sup1.cif

e-70-0o714-sup1.cif^{(17.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814011660/pk2524Isup2.hkl

e-70-0o714-Isup2.hkl^{(107.3KB, hkl)}

Click here for additional data file.^{(5.1KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814011660/pk2524Isup3.cml

CCDC reference: 1004303

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O4—H11⋯O3ⁱ	0.76	2.07	2.831 (2)	176
O4—H12⋯O3	0.82	2.21	2.994 (3)	160
C3—H3A⋯O1ⁱⁱ	0.97	2.39	3.269 (3)	151
C4—H4C⋯O4ⁱⁱⁱ	0.96	2.54	3.487 (3)	169

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

This work was supported by the Anhui Provincial Natural Science Foundation (1308085MB24) and the Educational Commission of Anhui Province of China (KJ2012A025).

supplementary crystallographic information

1. Comment

Benzothiazole, a small and simple heterocyclic molecule, has raised considerable interest. It can be used to synthesize some Schiff bases (Vicini et al., 2003), and other derivatives that are antimicrobial (Bondock et al., 2010) and bioactive (Paramashivappa et al., 2003). They have also been used in dye-sensitized solar cells (Sayama et al., 2002). Spurred by this, we synthesized 3-(2-methylbenzo[d]thiazol-3-ium-3-yl)propane-1-sulfonate (Fig. 1), which contains a sulfonic group, with the aim of increased solubility. The single-crystal structure contains one water molecule. Comparing with C₇H₅N₃O₂S₁·H₂O (Lynch, 2002), both of them are in a hydrogen-bonding network with water molecules. The water H atoms are connected with O atoms of sulfonic moieties and the molecules are interconnected, via hydrogen bonds (Table 1) [O4—H11···O3ⁱ, symmetry codes: (i) -x, -y + 1, -z + 1; C3—H3A···O1ⁱⁱ, symmetry codes: (ii) -x, y + 1/2, -z + 3/2; C4—H4C···O4ⁱⁱⁱ, symmetry codes: (iii) -x, y - 1/2, -z + 3/2]. There is a R²₄(8) ring formed by hydrogen-bonded water to O3—S1 interactions. Two characteristic O4—H12···O3 and O4—H11···O3ⁱ distances are 2.994 (3) Å and 2.831 (2) Å, respectively (Fig.2). In the crystal, inversion related (1-x,1-y,2-z) molecules are π-stacked with an interplanar separation of 3.3847 (2) Å. O—H···O hydrogen bonds link inversion-related (-x,1-y,1-z) molecules with a pair of water molecules to form R²₄(8) rings. The closest ring S···S contact is 3.4051 (15) Å between inversion-related (1-x,-y,2-z) molecules (Fig.3). The bond length between N1 and C5 [1.3216 (2) Å] indicates some double bond character and is conjugated with neighbouring bonds. The two distances of S2—C6 and S2—C5 are nearly the same [1.7327 (19) Å and 1.7024 (18) Å, respectively]. In addition, the large size of the S atom compared with N results in a reduction of the C5—S2—C6 angle [91.069 (8)°] compared with the C5—N1—C11 angle [114.001 (14)°] in thiazole ring. This reveals that the S atom might be using unhybridized p-orbitals for bonding (Muir et al., 1987).

2. Experimental

The title complex, 3-(2-methylbenzo[d]thiazol-3-ium-3-yl)propane-1-sulfonate, was prepared by mixing 2-methylbenzo[d]thiazole (1.49 g, 0.010 mol) with 1,2-oxathiolane 2,2-dioxide (1.47 g, 0.012 mol) in toluene (20 ml). The mixture was heated to reflux for 4 h. After the reaction was complete, the solution was cooled to room temperature. The mixture was filtered and washed with ethanol 3 times to give a white solid. Colorless block-shaped crystals were grown by slow evaporation an acetonitrile/ethanol mixture. ¹H NMR: (400 Hz, DMSO-d₆), d(p.p.m.): 8.43 (t, 2H), 7.90 (t, 1H), 7.80 (t, 1H), 4.90 (t, 2H), 3.20 (s, 3H), 2.65 (t, 2H), 2.15 (q, 2H).